CN108997771B - Dye with strong absorption and photo-thermal effect in near infrared region and preparation method and application thereof - Google Patents
Dye with strong absorption and photo-thermal effect in near infrared region and preparation method and application thereof Download PDFInfo
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- CN108997771B CN108997771B CN201810604372.3A CN201810604372A CN108997771B CN 108997771 B CN108997771 B CN 108997771B CN 201810604372 A CN201810604372 A CN 201810604372A CN 108997771 B CN108997771 B CN 108997771B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
- C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
- C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/10—The polymethine chain containing an even number of >CH- groups
- C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
Abstract
Dyes with strong absorption and photothermal effect in a near infrared region, a preparation method and application thereof, which belong to the technical field of fine chemical engineering. Compared with the conventional cyanine dye, the dye has longer wavelength, has absorption in a near-infrared first region and a near-infrared second region, can avoid various defects of the dye in a visible region during imaging, and can be used for various optical imaging of the near-infrared first region and the near-infrared second region; the strong absorption of the dye in the near infrared region can also be used for optical treatment in the near infrared region one and two.
Description
Technical Field
The invention relates to a long-wavelength dye with strong absorption and photothermal effect in a near infrared region I and a near infrared region II, a preparation method and application thereof, and belongs to the technical field of fine chemical engineering.
background
The development of fluorescence microscopy and fluorochromes has brought people closer to the microscopic cellular world, and with the advantage of fluorescence visualization, a vast array of excellent fluorochromes and probes have been developed, many of which have been commercialized. The absorption and emission wavelengths of the traditional fluorescent dye are in a visible region, and relatively few commercial dyes and kits reach a near infrared region. Although commercially available fluorescent dyes can meet some basic requirements, they have problems, such as strong absorption and scattering of visible fluorescence by cells, and decrease of collected fluorescence signals to some extent; meanwhile, strong autofluorescence exists in cells, and great interference is caused to detection and imaging to a certain extent; finally, due to the limited penetration of visible light, it is far less effective than near infrared fluorescent dyes in vivo imaging. Since the biological tissue has a lower light absorption capacity at the wavelength of 700-1700 nm than that of the visible region, the spectral band in this region is also called the biological spectroscopy window, wherein 700-900 nm is the near-infrared first optical window, and 1000-1700 nm is the near-infrared second optical window. Therefore, there is a need to develop a fluorescent dye that absorbs and emits in the near infrared region one and two to avoid the various drawbacks encountered in imaging.
Photothermal therapy, which converts near infrared light into heat by means of fluorescent dyes, is a hot spot in cancer treatment in recent years, unlike conventional chemotherapeutic drugs. When the heat is accumulated to a certain degree, a killing effect on cancer cells is formed. Common near-infrared thermal sensitizers include indocyanine green (ICG), carbon nanotubes, gold nanorods, etc., but the ICG has the disadvantages of poor light stability and low photo-thermal conversion efficiency, and the carbon nanotubes and the gold nanorods have the disadvantages of poor biocompatibility, so it is necessary to develop a class of dye molecules having strong absorption and photo-thermal effects in the first and second near-infrared regions to avoid the above disadvantages.
disclosure of Invention
the object of the present invention is to prepare a class of dyes that can have strong absorption and photothermal effects in the near infrared first and second optical windows. Wherein, the dye absorption spectrum is between 700-900 nm and can be applied to near-infrared one-zone optical imaging, photoacoustic imaging, photothermal therapy, photodynamic therapy and the like; the dye absorption spectrum is between 1000-1700 nm and can be applied to optical imaging of a near-infrared two-region, photoacoustic imaging and near-infrared two-region optical treatment. The dye can avoid a series of defects faced by commercial dyes, and has wide application in aspects of biological imaging, optical treatment and the like.
the present invention provides long wavelength dyes and derivatives of the general formula:
Wherein the content of the first and second substances,
r1 is a tertiary amine attached to the parent with an N atom, R1 has the structure
When R1 is selected, it is attached to the parent atom in a manner such that the N atom is attached to the parent, for example:
X- ═ PF 6-or BF 4-or Cl-or Br-or I-or NO 3-or SO 42-or ClO 4-or CH3 COO-or CH3SO 3-or CF3SO3-
the preparation process of the long-wavelength dye of the invention is as follows:
First, oxonium ion W is synthesized, and the oxonium ion W is condensed with different condensing agents (S1, S2, S3) to obtain corresponding long-wavelength dyes.
r1 is a tertiary amine attached to the parent with an N atom, R1 has the structure
When R1 is selected, its connection mode includes, for example:
X- ═ PF 6-or BF 4-or Cl-or Br-or I-or NO 3-or SO 42-or ClO 4-or CH3 COO-or CH3SO 3-or CF3SO3-
A preparation method of a long-wavelength dye and a derivative thereof comprises the following steps:
(1) Synthesis of oxonium ion W: adding concentrated sulfuric acid into cyclohexanone (cyclopentanone and cycloheptanone) under ice bath, adding benzaldehyde or ketone substituted by corresponding 4-site amino group and 2-site hydroxyl group, and heating to 90 deg.C for reaction for 1.5 h. After cooling to room temperature, the product was poured into a large amount of ice to precipitate a red solid, which was filtered off with suction and dried for direct use in the next step.
(2) Synthesis of dye: mixing the oxonium ion W in the step (1) with corresponding condensing agent (S1, S2, S3) in the presence of acetic anhydride or volume ratio of 1: 1 n-butanol: refluxing in benzene, cooling to room temperature, washing with water, extracting, drying, and separating by column chromatography.
The invention has the beneficial effects that: 1) the absorption wavelength of the compound is in a near infrared region, and the absorption and emission of a part of compounds can reach a near infrared region II, so that autofluorescence and scattering phenomena in a living body can be completely avoided. 2) The compounds can absorb near infrared fluorescence, the maximum absorption wavelength of the compounds in example 1 is 890nm (in dichloromethane), and the maximum absorption wavelength of the compounds in example 15 (originally example 10, now changed to 15) is 980nm (in dichloromethane), and the near infrared region is achieved. In the embodiment 1, the dye absorbs near infrared light and is converted into heat, and the temperature can be increased from 23.9 ℃ to 54.9 ℃; as can be seen from FIG. 4, the temperature of the dye in example 15 reached 55.4 ℃ from 22.5 ℃ after absorbing near infrared light. Has great application prospect in the aspect of photothermal therapy.
ICG has the disadvantages of poor light stability and low photo-thermal conversion efficiency, and carbon nano tubes and gold nano rods have the disadvantage of poor biocompatibility, and compared with ICG, the carbon nano tubes and the gold nano rods, the dye in the invention has longer absorption, and the light stability is greatly improved compared with ICG; the dye of the invention belongs to organic micromolecular dye, and the biocompatibility of the dye is superior to that of the conventional carbon nano tube and gold nano rod.
drawings
FIG. 1 is an absorption spectrum of the compound of example 1.
FIG. 2 is an absorption spectrum of the compound in example 15.
FIG. 3 is a graph showing the temperature rise by light irradiation of the compound in example 1.
FIG. 4 is a graph showing the temperature rise by light irradiation of the compound in example 15.
Detailed Description
the following detailed description of the embodiments of the invention refers to the accompanying drawings.
the invention is illustrated but not limited by the following examples in which all parts and percentages are by weight unless otherwise indicated.
Example 1
Oxonium salt W1(0.2mmol), condensing agent S1(0.09mmol) and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked by dot plate. The product was purified by column separation, HRMS (M +): 521.3160.
Example 2
Onium salt W2(0.2mmol), condensing agent S1(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 493.2850.
Example 3
onium salt W3(0.2mmol), condensing agent S1(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 549.3476.
Example 4
onium salt W4(0.2mmol), condensing agent S1(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 465.2537.
Example 5
onium salt W5(0.2mmol), condensing agent S1(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 569.3163.
example 6
onium salt W6(0.2mmol), condensing agent S1(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 489.2537.
Example 7
Onium salt W7(0.2mmol), condensing agent S1(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 517.2850.
example 8
Onium salt W8(0.2mmol), condensing agent S1(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 761.3583.
example 9
Onium salt W9(0.2mmol), condensing agent S1(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 733.3272.
example 10
Onium salt W10(0.2mmol), condensing agent S1(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 673.3789.
Example 11
onium salt W11(0.2mmol), condensing agent S1(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 571.3068.
Example 12
Onium salt W12(0.2mmol), condensing agent S1(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 729.2959.
Example 13
Onium salt W13(0.2mmol), condensing agent S1(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 809.3589.
example 14
Onium salt W14(0.2mmol), condensing agent S1(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 757.3271.
Example 15
onium salt W1(0.2mmol), condensing agent S2(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 547.3319.
Example 16
onium salt W2(0.2mmol), condensing agent S2(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 519.3006.
example 17
onium salt W3(0.2mmol), condensing agent S2(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 575.3632.
Example 18
Onium salt W11(0.2mmol), condensing agent S2(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 597.3224.
Example 19
onium salt W6(0.2mmol), condensing agent S2(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 515.2693.
example 20
Onium salt W7(0.2mmol), condensing agent S2(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 543.3006.
Example 21
Onium salt W4(0.2mmol), condensing agent S2(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 491.2693.
Example 22
Onium salt W5(0.2mmol), condensing agent S2(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 595.3319.
Example 23
Onium salt W13(0.2mmol), condensing agent S2(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 835.3742.
example 24
Onium salt W15(0.2mmol), condensing agent S2(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 731.3116.
Example 25
onium salt W8(0.2mmol), condensing agent S2(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 787.3742.
example 26
onium salt W9(0.2mmol), condensing agent S2(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 759.3429.
Example 27
onium salt W10(0.2mmol), condensing agent S2(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 670.3554.
Example 28
onium salt W12(0.2mmol), condensing agent S2(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 755.3116.
Example 29
Onium salt W14(0.2mmol), condensing agent S2(0.09mmol), and sodium acetate (0.2mmol) were mixed uniformly, 5mL of acetic anhydride was added, reaction was carried out at 140 ℃ for 120min, and the progress was checked on a dot-panel. The product was purified by column separation, HRMS (M +): 783.3429.
example 30
onium salt W1(0.2mmol) and condensing agent S3(0.09mmol) were mixed well, 5mL of n-butanol/benzene (1: 1) were added, reaction was carried out at 150 ℃ for 4 hours, and the progress was checked on a dot plate. The product was purified by column separation, HRMS (M +): 647.3399.
Example 31
Onium salt W2(0.2mmol) and condensing agent S4(0.09mmol) were mixed well, 5mL of n-butanol/benzene (1: 1) were added, reaction was carried out at 150 ℃ for 4 hours, and the progress was checked on a dot plate. The product was purified by column separation, HRMS (M +): 605.2929.
Example 32
onium salt W2(0.2mmol) and condensing agent S3(0.09mmol) were mixed well, 5mL of n-butanol/benzene (1: 1) were added, reaction was carried out at 150 ℃ for 4 hours, and the progress was checked on a dot plate. The product was purified by column separation, HRMS (M +): 619.3086.
Example 33
Onium salt W1(0.2mmol) and condensing agent S5(0.09mmol) were mixed well, 5mL of n-butanol/benzene (1: 1) were added, reaction was carried out at 150 ℃ for 4 hours, and the progress was checked on a dot plate. The product was purified by column separation, HRMS (M +): 691.2894.
example 34
Onium salt W3(0.2mmol) and condensing agent S3(0.09mmol) were mixed well, 5mL of n-butanol/benzene (1: 1) were added, reaction was carried out at 150 ℃ for 4 hours, and the progress was checked on a dot plate. The product was purified by column separation, HRMS (M +): 675.3712.
example 35
onium salt W11(0.2mmol) and condensing agent S3(0.09mmol) were mixed well, 5mL of n-butanol/benzene (1: 1) were added, reaction was carried out at 150 ℃ for 4 hours, and the progress was checked on a dot plate. The product was purified by column separation, HRMS (M +): 697.3304.
example 36
onium salt W5(0.2mmol) and condensing agent S3(0.09mmol) were mixed well, 5mL of n-butanol/benzene (1: 1) were added, reaction was carried out at 150 ℃ for 4 hours, and the progress was checked on a dot plate. The product was purified by column separation, HRMS (M +): 695.3399.
Example 37
onium salt W4(0.2mmol) and condensing agent S3(0.09mmol) were mixed well, 5mL of n-butanol/benzene (1: 1) were added, reaction was carried out at 150 ℃ for 4 hours, and the progress was checked on a dot plate. The product was purified by column separation, HRMS (M +): 591.2773.
Example 38
Onium salt W6(0.2mmol) and condensing agent S3(0.09mmol) were mixed well, 5mL of n-butanol/benzene (1: 1) were added, reaction was carried out at 150 ℃ for 4 hours, and the progress was checked on a dot plate. The product was purified by column separation, HRMS (M +): 615.2773.
Example 39
Onium salt W7(0.2mmol) and condensing agent S3(0.09mmol) were mixed well, 5mL of n-butanol/benzene (1: 1) were added, reaction was carried out at 150 ℃ for 4 hours, and the progress was checked on a dot plate. The product was purified by column separation, HRMS (M +): 643.3086.
Example 40
Onium salt W15(0.2mmol) and condensing agent S3(0.09mmol) were mixed well, 5mL of n-butanol/benzene (1: 1) were added, reaction was carried out at 150 ℃ for 4 hours, and the progress was checked on a dot plate. The product was purified by column separation, HRMS (M +): 831.3195.
EXAMPLE 41
Onium salt W8(0.2mmol) and condensing agent S3(0.09mmol) were mixed well, 5mL of n-butanol/benzene (1: 1) were added, reaction was carried out at 150 ℃ for 4 hours, and the progress was checked on a dot plate. The product was purified by column separation, HRMS (M +): 887.3821.
Example 42
Onium salt W9(0.2mmol) and condensing agent S3(0.09mmol) were mixed well, 5mL of n-butanol/benzene (1: 1) were added, reaction was carried out at 150 ℃ for 4 hours, and the progress was checked on a dot plate. The product was purified by column separation, HRMS (M +): 859.3508.
Example 43
onium salt W9(0.2mmol) and condensing agent S4(0.09mmol) were mixed well, 5mL of n-butanol/benzene (1: 1) were added, reaction was carried out at 150 ℃ for 4 hours, and the progress was checked on a dot plate. The product was purified by column separation, HRMS (M +): 845.3352.
example 44
Onium salt W10(0.2mmol) and condensing agent S3(0.09mmol) were mixed well, 5mL of n-butanol/benzene (1: 1) were added, reaction was carried out at 150 ℃ for 4 hours, and the progress was checked on a dot plate. The product was purified by column separation, HRMS (M +): 799.4025.
Example 45
onium salt W12(0.2mmol) and condensing agent S3(0.09mmol) were mixed well, 5mL of n-butanol/benzene (1: 1) were added, reaction was carried out at 150 ℃ for 4 hours, and the progress was checked on a dot plate. The product was purified by column separation, HRMS (M +): 855.3195.
example 46
Onium salt W14(0.2mmol) and condensing agent S3(0.09mmol) were mixed well, 5mL of n-butanol/benzene (1: 1) were added, reaction was carried out at 150 ℃ for 4 hours, and the progress was checked on a dot plate. The product was purified by column separation, HRMS (M +): 883.3508.
Example 47
Onium salt W13(0.2mmol) and condensing agent S3(0.09mmol) were mixed well, 5mL of n-butanol/benzene (1: 1) were added, reaction was carried out at 150 ℃ for 4 hours, and the progress was checked on a dot plate. The product was purified by column separation, HRMS (M +): 935.3821.
Example 48
dye (0.1mmol) and aniline (0.2mmol) are mixed evenly, 25mL of acetonitrile is added, reaction is carried out at room temperature, and the progress is detected by a dot-plate method. The product was purified by column separation, HRMS (M +): 704.4211.
Example 49
dye (0.1mmol), phenol (0.2mmol) and potassium carbonate (0.1mmol) are mixed evenly, 25mL of acetonitrile is added for reaction at room temperature, and the progress is detected by a dot-plate method. The product was purified by column separation, HRMS (M +): 705.40511.
example 50
dye (0.1mmol), phenothiol (0.2mmol), and potassium carbonate (0.1mmol) were mixed well, 25mL acetonitrile was added, the reaction was carried out at 50 ℃ and the progress was checked on a dot-plate. The product was purified by column separation, HRMS (M +): 721.3822.
example 51
dye (0.1mmol) and aniline (0.2mmol) are mixed evenly, 25mL of acetonitrile is added, reaction is carried out at room temperature, and the progress is detected by a dot-plate method. The product was purified by column separation, HRMS (M +): 662.3741.
example 52
dye (0.1mmol), phenol (0.2mmol) and potassium carbonate (0.1mmol) are mixed evenly, 25mL of acetonitrile is added for reaction at room temperature, and the progress is detected by a dot-plate method. The product was purified by column separation, HRMS (M +): 663.3581.
Example 53
dye (0.1mmol), phenothiol (0.2mmol), and potassium carbonate (0.1mmol) were mixed well, 25mL acetonitrile was added, the reaction was carried out at 50 ℃ and the progress was checked on a dot-plate. The product was purified by column separation, HRMS (M +): 679.3353.
example 54
dye (0.1mmol) and butyl amine (0.2mmol) are mixed evenly, 25mL of acetonitrile is added for reaction at room temperature, and the progress is detected by a dot-plate method. The product was purified by column separation, HRMS (M +): 684.4524.
Example 55
dye (0.1mmol) and butyl amine (0.2mmol) are mixed evenly, 25mL of acetonitrile is added for reaction at room temperature, and the progress is detected by a dot-plate method. The product was purified by column separation, HRMS (M +): 642.4054.
example 56
dye (0.1mmol) and N-methyl piperazine (0.2mmol) are mixed uniformly, 25mL of acetonitrile is added, reaction is carried out at room temperature, and the progress is detected by a dot-plate method. The product was purified by column separation, HRMS (M +): 711.4133.
Example 57
dye (0.1mmol) and N-methyl piperazine (0.2mmol) are mixed uniformly, 25mL of acetonitrile is added, reaction is carried out at room temperature, and the progress is detected by a dot-plate method. The product was purified by column separation, HRMS (M +): 669.4163.
example 58
dye 1100 mg was dissolved in 50mL of ethanol, and 20 times the amount of sodium sulfate was dissolved in an appropriate amount of water, added to the dye, stirred overnight at 25 deg.C, filtered to remove insoluble salts, the solvent was spin-dried, and separated on a column. HRMS (M +): 521.3160.
example 59
The test method of dye absorption spectrum comprises the following steps: taking the compounds in example 1 and example 10 as examples, 10uM of mother liquor was prepared from the dye with DMSO, and the absorption spectra in different solvents were measured. The maximum absorption wavelength of 890nm (in dichloromethane) for the compound of example 1 can be seen from fig. 1, and the maximum absorption wavelength of 980nm (in dichloromethane) for the compound of example 10 has been reached in the near infrared region from fig. 2.
example 60
dye illumination heating experiment: using the compounds of example 1 and example 10 as examples, 10uM stock solutions of the dyes were made up in DMSO. The dye was dispersed in deionized water to a final concentration of 40 uM. The sample was irradiated with 808nm laser at power of 1W for 5min, and the temperature was photographed using a near infrared thermal imager. As can be seen from FIG. 3, the dye in example 1 absorbs near infrared light and then converts the light into heat, and the temperature can be raised from 23.9 ℃ to 54.9 ℃; as can be seen from FIG. 4, the temperature of the dye in example 15 reached 55.4 ℃ from 22.5 ℃ after absorbing near infrared light.
Claims (3)
1. The dye with strong absorption and photothermal effect in the near infrared region is characterized in that the structural general formula of the dye is as follows:
wherein h =0,1, 2; i =0, 1;
r1 has the structure
wherein: n =0-18, m =0-18;
X-is an anion which is PF 6-or BF 4-or Cl-or Br-or I-or NO 3-or SO 42-or ClO 4-or CH3 COO-or CH3SO 3-or CF3SO 3-;
the total number of positive charges carried by the cations in the dye is equal to the total number of negative charges carried by the anions.
2. The method for preparing the dye with strong absorption and photothermal effect in the near infrared region according to claim 1, comprising the steps of:
Firstly, synthesizing oxonium ions W, and condensing the oxonium ions W with a condensing agent S1, S2 or S3 to obtain corresponding long-wavelength dye;
the synthetic route of the dye is as follows:
Wherein: r1, R2, R3, h, i, n, m and X-are as defined in the general formula in claim 1.
3. The use of a dye having strong absorption and photothermal effect in the near infrared region according to claim 1, wherein: the dye is applied to near-infrared first-region and second-region optical imaging and optical treatment.
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| CN115745939A (en) * | 2022-10-14 | 2023-03-07 | 广西大学 | Novel rhodamine dye with near-infrared two-region wavelength, and preparation method and application thereof |
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